Control of insects and nematodes with vinyl phosphate derivatives

ABSTRACT

VINYL PHOSPHATE DERIVATIVES,INCLUDING PARTICULARLY COMPOUNDS OF THE FORMULA   1-(R2-O-P(=O)(-R1)-O-C(=CH-CL)-)PYRROLIDIN-2-ONE   IN WHICH (A) R1 IS METHOXY AND R2 IS METHYLOT (B) R1 IS ETHOXY AND R2 IS ETHYL, ARE USEFUL AS PESTICIDAL AGENTS, PARTICULARLY IN THE CONTROL OF INSECTS AND NEMATODES.

United. States Patent 3,814,798 Patented June 4, 1974 3,814,798 CONTROL OF INSECTS AND NEMATODES WITH VINYL PHOSPHATE DERIVATIVES Henry Martin and Josef Drabek, Basel, Switzerland, assignors to Ciba-Geigy AG, Basel, Switzerland No Drawing. Original application May 18, 1970, Ser. N 0. 38,570, now Patent No. 3,705,904, dated Dec. 12, 1972. Divided and this application Dec. 7, 1972, Ser. No. 314,201 Claims priority, applicationSwitzerland, May 19, 1969,

- 7,679/69; July 22, 1969, 11,193/69 Int. Cl. A01n 9/22, 9/24, 9/36 US; Cl. 424-200 6 Claims ABSTRACT F THE'DISCLOSURE Vinyl phosphate derivatives, including particularly compounds of the formula v RzO-%l"-OCl=CHCl 0. I, The

in which (a) R is methoxy and R is methyl or (b) R is ethoxy and R is ethyl, are useful as pesticidal agents, particularly in the control of insects and nematodes.

in which R represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, R represents an alkyl group having 1 to 4 carbon atoms, X represents a CO-- or an SO group and Y represents a hydrogen or a chlorine atoms, R representing an alkyl group having 1 to 4 carbon atoms when Y is a hydrogen atom, and R represents an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or a phenyl radical substituted by a halogen or an alkyl group having 1 'to 4 carbon atoms, or a hydrogen atom when X is a CO group, and in which R, and R together with the symbols N and X, can also constitute a five-membered to sevenmembered heterocycle containing at least one CO or SO: group, or in which, when Y is a chlorine atom, R represents an alkyl group having 1 to 4 carbon atoms or a phenyl radical that may be unsubstituted or substituted by a halogen or an alkyl group having 1 to 4 carbon atoms, and R provided R represents an alkyl group, represents a phenyl radical that may be unsubstituted or substituted by a halogen, an alkyl group having 1 to 4 carbon atom and/or N0 whereas, on the other hand, R provided R represents a phenyl radical that may be substituted, represents an alkyl group having 1 to 4 carbon atoms, or a hydrogen atom when X is a CO group, or R and R together with the symbols N and X, can constitute a five-membered to seven-membered heterocycle containing at least two carbonyl groups or a heterocycle fused to a benzene nucleus or to a cyclohexyl ring.

The term alkyl group containing 1 to 4 carbon atoms" as used herein refers primarily to methyl, ethyl or propyl group, the term alkoxy group containing 1 to 4 carbon atoms refers to methoxy, ethoxy or propoxy groups, and the term cycloalkyl group containing 3 to 6 carbon atoms refers, in particular, to cyclopropyl and cyclohexyl groups. The term halogen as used herein refers to fluorine, chlorine, bromine and iodine, but especially to chloride or bromine.

An important group belong to the series of compounds represented by Formula I are those corresponding to Formula 11 in which R, represents a methyl, ethyl, methoxy or ethoxy group, R'g represents a methyl or ethyl group, X represents a CO- or an SO group, but especially a --OO-- group, R represents an alkyl group having 1 to 4 carbon atoms and R, represents an alkyl group having 1 to 4 carbon atoms, a cyclopropyl group or a phenyl radical substituted by a halogen atom or an alkyl group having 1 to 4 carbon atoms, or may represent a hydrogen atom when X is a CO--- group, or in which R' and R',, together with the symbols N and X, can form a fivemembered to seven-membered heterocycle containing at least one carbonyl group, with X representing CO-'--.

Another important group belonging to the series of compounds represented by Formula I are those corresponding to Formula HI in which R, represents a methyl, ethyl, methoxy or ethoxy group, R, represents a methyl or ethyl group, X represents a CO or 40 group, R represents an alkyl group having 1 to 4 carbon atoms or a phenyl radical that may be unsubstituted or substituted by a halogen atom or an alkyl group containing 1 to 4 carbon atoms, and R".;, provided R is an alkyl group, represents a phenyl radical substituted by a chlorine atom, a methyl group and/or N whereas R" when R is a phenyl radical that may be substituted, represents an alkyl group containing 1 to 4 carbon atoms, or is a hydrogen atom when X is a CO- group, or in which R and R".,, together with the substituent N and the substituent X constituting a -CO group, form a five-membered to seven-membered heterocycle containing at least two carbonyl groups or a heterocycle fused to a benzene nucleus.

An important sub-group of compounds belonging to the series represented by Formula III are those in which R' represents a methoxy or an ethoxy group.

The new compounds of Formula I can be used as pesticides together with one or more of the following additives: a carrier, a solvent, a diluent, a dispersing agent, an emulsifying agent, a thickening agent, an adhesive, a wetting agent and/or a fertilizer and,'if necessary, a known pesticide or a bait.

The advantage of the new compounds, in additon to their broad-spectrum action in combating various plant and animal pests, is their stability towards alkalis, which makes them eminently suitable for use in cattle dips, for example, for the control of ectoparasites, for application in rice fields and, in general, for application in soil, for example, for the control of soil-dwelling insects, acarids and nematodes and for the control of certain bacteria, fungi and weeds.

The animal pests include, in particular, insects and members of the order acarina, for example, mites and ticks, including the different stages of metamorphosis, that is to say, eggs, larvae, nymphs and pupae.

The compounds of Formula I can be used, for example, against all harmful insects, for example, aphids, for example, the potato aphid (Myzus persicae) and the black bean aphid (Doralis fabae); shield lice, for example, Aspidiotus hederae, lecanium hesperz'dium and Pseudococcus maritimus; thysanoptera, for example, Hercinothrips femoralis, and bugs, for example, the beet leaf bug (Piesma quadrata) and the bedbug (Cimex lectularius); butterfly larvae, for example, Plutella maculipennis and Lymantria dispar; beetles, for example, corn weevils (Sitophilus granarius) and Colorado beetles (Leptinotarsa decomlineata), and also the soil-dwelling larvae, for example, wire worms (Agriotes sp.) and cockchafer larvae (Melolontha melolomha); cockroaches, for example, the German cockroach (Blattella germanica); the cricket (Gryllus domesticus); termites, for example, Reticulitermes; hymenoptera, for example, ants; lepidoptera, for example, Chilo suppressalis; diptara, for example, the fruit fly Drosophila melanogaster, the Mediterranean fruit fly Ceratitis capitata, the housefly (Musca domestica) and lgnats, for example, Aedes aegypti and Anopheles stepensz.

The compounds of Formula I are also specially efficient at controlling members of the order acarina, for example, Eulaelaps, Echinolaelaps, Laelaps, Haemoganmasus, Dermanyssus, Ornithonyssus, Allodermanyssus, especially Allodermanyssus sanguineus, Pneumonyssus, Amblyomma, Aponomma, Boophilus, Dermancentor, Haemophysalis, Hyalomma, Ixodes, Margaropus, Rhipicephalus, Ornithodirus; Otobius, Chelyletidae, for example, Cheyletus, Psorergates, Demodicidae, Trombiculidae, for example, Trombicula, Eutrombicula, Schtingastia, Acomatacurus, iNeoschongastia, Euschongastia, Sarcoptiformes, for example, Notoedres, Sarcoptes, Knemidokoptes, Psoroptidae, for example, Psoroptes, Choripotes, Otodectes or Tetranychidae, for example, Tetranychus telarius; Tetranychus urticae.

Nematodes that may be mentioned, particularly phytopathogenic nematodes, are those belonging to the following orders:

Aphelenchoides, for example, Aphelenchus ritzemabosi, A phelenchus fragariae, A phelenchus oryzae, Ditylenchoides, for example, Ditylenchus dipsaci, meloidogynes, for example, Meloidogyne arenaria, Meloidogyne incognita, cyst-forming nematodes (heterodera), for example, Heterodera rostochiensis, Heterodera schachtii, and also root nematodes, for example, Paratylenchus, Rotylenchus, Xiphinema and Rhadopholus.

Pesticidal preparations, generally containing 0.1 to percent by weight, preferably 1 to 85 percent by Weight, of the new compounds of Formula I (or Formulae II or III) can be made up in a Wide variety of forms, for example, in the form of dry or moist preparations or as liquids or solids. Shaped carriers such as fly-dishes, flypapers, paper strips or granules can be impregnated with the active principles. The active principles can also be transformed into a gas phase by means of sprays.

However, they can also be used in almost pure form without additives when applied from spraying devices producing a fine enough spray. The main means of application of this kind would be spraying from aircraft.

The solvents used in the preparation of solutions of compounds of Formula :I that can be used directly as sprays are, for example, mineral oil fractions having a high to medium boiling range, for example, Diesel oil or kerosene, coal-tar oil and oils of vegetable or animal origin, as well as hydrocarbons, for example, alkylated naphthalenes, tetrahydronaphthalene, if necessary, in conjunction with xylene mixtures, cyclohexanols and ketones, and also chlorinated hydrocarbons, for example, trichloroethane, trichloroethylene or triand tetra-chlorobenzenes. It is advantageous to use organic solvents having a boiling point above C.

The aqueous preparations are advantageously prepared by the addition of water to emulsion concentrates, pastes or wettable powders. Suitable emulsifying or dispersing agents are non-ionic products, for example, condensation products of aliphatic alcohols, amines or carboxylic acids having a long-chain hydrocarbon radical containing about 10 to 20 carbon atoms and ethylene oxide, for example, the condensation product of octadecyl alcohol and 25 to 30 mols of ethylene oxide, or the condensation product of commercial oleylamine and 15 mols of ethylene oxide or the condensation product of dodecylmercaptan and 12 mols of ethylene oxide. The following are examples of suitable anionic emulsifying agents: the sodium salt of dodecyl alcohol sulphuric acid ester, the sodium salt of dodecylbenzenesulphonic acid, the potassium or triethanolamine salt of oleic acid or abietic acid or mixtures of these acids, or the sodium salt of a petroleum sulphonic acid. Suitable cationic dispersing agents are quaternary ammonium compounds, for example, cetylpyridinium bromide or dihydroxyethylbenzyldodecylammonium chloride.

Dusting and strewing preparations can be prepared by using solid carriers, for example, talcum, kaolin, bentonite, calcium carbonate, calcium phosphate, and also charcoal, cork meal, wood flour and other materials of vegetable origin. It is also highly advantageous to make preparations in granular form. The preparations in their various forms can also be provided with substances that improve dispersion, adhesion, rain-resistance and penetration; substances of this kind are, for example, fatty acids, resins, glues, casein or alginates.

The compounds of the invention can be used either alone or together with known pesticides, especially insecticides, acaricides, nematicides, bactericides, fungicides, and so forth.

The action of the phosphorus compounds of the invention can be enhanced by synergists. Suitable substances are, for example, sesamin, sesamex, piperonyl cyclonenes, piperonyl butoxide, piperonal bis[2 (2 butoxyethoxy) ethyl]acetate, sulphoxides, propyl isomers, N-(Z-ethylhexyl)-5-norbornene-2,3-dicarboxamide, octachlorodipropylether, 2-nitrophenylpropargylether, 4-chloro-2-nitrophenylpropargylether and 2,4,5-trichlorophenylpropargylether.

Known insecticides, acaricides ior-nematicides can be added to broaden .the spectrum: of action of the compounds of the invention. 1 t i v The following are given as examples:

PHOSPHORIC ACID DERIVATIVES bis-OO-diethylphosphoric acid anhydride (TEPP) 0,0,0,0-tetrapropyldithiopyrophosphate dimethyl (2,2,2-trichloro-1 -hydroxyethyl) pho sphonate (Trichrorfon) 1,2-dibromo-2,Z-dichloroethyldimethylphosphate (Naled) 2,2-dichlorovinyldimethylphosphate (Dichlorfos) 2-methoxycarbamyl-1-methy1vinyldimethylphosphate (Mevinphos) dimethyl-l-methyl-Z-(methylcarbamoyl)vinylphosphate cis (Monocrotophos) 3- dimethoxyphosphinyloxy) N-methyl-N-methoxycis-crotonamide 3 dimethoxyphosphinyloxy) -N,N-dimethyl-ciscrotonamide Dicrotophos) 2-chloro-2-diethylcarbamoyl-l-methylvinyldimethylphosphate (Phosphamidon) 0,0diethy1-O(or S) -2-(ethylthio)-ethylthiophosphate (Demeton) S-ethylthioethyl-0,0-dimethyl-dithiophosphate (Thiometon) 0,0-diethyl-S-ethylmercaptomethyld'ithiophosphate (Phorate) 0,0-diethy1-S-2- (ethylthio ethyl] dithiophosphate (Disulfoton) 0,0-dimethy1-S-2- (ethylsulphinyl) ethylthiophosphate (Oxydemetonmethyl) 0,0-dimethyl-S-( 1,2-dicarethoxyethyl) dithiophosphate (Malathion) 0,0,0,=O-tetra-ethy1-S, S'-methylene-bis- [dithiopho sphate] (Ethion) O-ethyl-S,S-dipropyldithiophosphate 0,0-dimethy1-S-(N-methyl-N-formylcarbamoy1- methyl)-dithiophosphate (Formotion) 0,0-dimethyl-S- (N methylcarbamoylmethyl) -dithiophosphate (Dimethat) 0,0-dimethyl-S-(N-ethylcarbamoylmethyl)dithiophosphate (Ethoat-methyl) 0,0-diethy1$- N-isopropylcarbamoylmethyl) -dithiophosphate (Prothoat) S-N-( l-cyano-l-methylethyl) carbamoylmethyldiethylthiophosphate (Cyanthoat) S- (Z-acetamidoethyl -0,0-dimethyldithiophosphate hexamethylphosphoric acid triamide (HEMPA) 0,0-dimethyl-O-para-nitrophenylthiophosphate (Parathion-methyl) 0,0-diethyl-O-para-nitrophenylthiophosphate (Parathion) O-ethyl-O-para-nitrophenylphenylthiophosphonate ('EPN) 0,0-dimethy1-O-(4-nitro-meta-toly1) thiopho sphate Fenitrothion) 0,0-dimethyl-O- (2-chloro-4-nitrophenyl) thiopho sphate (Dicapthon) 0,0-dimethyl-O-para-cyanophenylthiophosphate (Cyanox) O-ethyl-O-para-cyanophenylphenylthiophosphonate 0,0-diethyl-O-2,4-dichlorophenylthiophosphate (Dichrofenthion) 0-2,4-dichlorophenyl-O-methylisopropylamidothiophosphate 0,0-dimethyl-O-2,4,S-trichlorophenylthiophosphate (Ronnel) O-ethyl-0-2,4,5-trichlorophenylethylthiophosphonate (Trichloronat) 0,0-dimethyl-O-2,5-dichloro-4-bromophenylthiophosphate (Bromophos) 0,0-diethyl-O-2,5-dichloro-4-bromophenylthiophosphate (Bromphos-ethyl) 0,0-dimethyl-O-(2,5-dich1oro-4-iodophenyl)-thiophosphate (Iodofenphos) 4-tert. butyl-2-chlorophenyl-N-methyl-O-methylamidophosphate (Crufomat) dimethyl-para- (methylthio phenylphosphate 0,0-dimethyl-O-(3-methyl-4-methylmercaptophenyl) thiophosphate Fenthion) isopropylamino-O-ethyl-O- (4-methylmercapto-3-methylpheny1)-phosphate 0,0-diethy1-O-para-[ (methylsu1phyny1)phenyl] -thiophosphate (Fensulfothion) 0,0-dimethyl-O-para-sulphamidophenylthiophosphate 0- [para- (dimethylsulphamido phenyl] 0,0-dimethy1- thiophosphate (Famphur) 0,0,0,0'-tetramethy1-0,0'-thiodi-para-phenylenethiophosphate 0- (para- (para-chlorophenylazophenyl) 0,0-dimethy1- thiophosphate (Azothoat) O-ethyl-S-phenylethy1dithiophosphonate O-ethyl-S-4-chlorophenylethyldithiophosphonate O-isobutyl-S-para-chlorophenylethyldithiophosphonate 0,0-dimethyl-S-para-chlorophenylthiophosphate 0,0-dimethyl-S-(para-chlorophenylthiomethyl)-dithiophosphate 0,0-diethyl-para-chlorophenylmercaptomethyldithiophosphate (Carbophenothion) 0,0-diethyl-S-para-chlorophenylthiomethylthiophosphate O, O-dimethyl-S- (carbethoxyphenylmethyl) dithiophosphate (Phenothoat) 0,0-diethy1-S-(carbofluoroethoxyphenylmethyl)-dithiophosphate 0,0-dimethyl-S- (carboisopropoxyphenyhnethyl) -dithiophosphate 0,0-dimethyl-O-(alpha-methylbenzyl-3-hydroxycrotonyl) -phosphate 2-chloro- 1- (2,4-dichlorophenyl vinyldiethylphosphate (Chlorfenvinphos) 2-ch1oro- 1- (2,4, 5 -trichloropheny1) vinyldimethylphosphate 0- (2-chloro-1- (2,5-dichlorophenyl) vinyl-0,0-diethylthiophosphate phenylglyoxylonitriloxime-0,0-diethylthi0ph0sphate (Phoxim) 0,0-diethy1-O-(3-ch1oro-4-methy1-2-oxo-2-H-l-benzopyran-7-yl)-thiophosphate (Coumaphos) 0,0-diethy1-7-hydroxy-3,4-tetramethylenecoummarinylthiophosphate (Coumithoat) 2, 3-para-dioxanedithiol-S,S-bis(0,0-diethy1dithiophosphate) (Dioxathion) 2-methoxy-4-H-1,3,2-benzodioxaphosphorine-Z-sulphide 0,0-diethyl-O-(5-pheny1-3-isooxyzolyl)thiophosphate S- (6-ch1oro-2-oxo-3-benzoxazo1inyl)methyl] 0,0-diethyldithiophosphate (Phosalon) 2- (diethoxyphosphynylimino) -4-methyl-1 ,3-dithiolan 0,0-dimethyl-S- [2-methoxy-1,3 ,4-thiadiaz0l-5- (4H) onyl- (4) -methyl] dithiophosphate tris- (Z-methyll-aziridinyl) -phosphine oxide (Metepa) 0,0-dirnethyl-S-phthalimidomethyldithiophosphate S- (2-chlorol-phthalimidoethyl) -0,0-diethyldithiophosphate N-hydroxynaphthalimidodiethylphosphate dimethy1-3,5,6-trichloro-2-pyridylphosphate I 0,0-dimethy1-O- (3,5 ,6-trichloro-2-pyridyl) thiophosphate 0,0-diethyl-O- 3,5,6-trichloro-2-pyridyl thiophosphate 0,0-diethyl-O-Z-pyrazinylthiophosphate (Thionazin) 0,0-diethy1-O- (2-isopropyl-4-methyl-6-pyrimidyl) thiophosphate (Diazinon) 0,0-diethyl-O- Z-quinoxylyl) thiophosphate 0,0-dimethyl-S- (4-oxo-1,2,3-benzotriazin-3 (4H) -ylmethyD-dithiophosphate (Azinphosmethyl) 0,0-diethyl-S-(4-oxo-1,2,3-benzotriazin-3 (4H) -ylmethy1)-dithiophosphate (Azinphosaethyl) 9 6,7,8,9,10,IO-hexachloro-1,5,5a,6,9,9u-hexahydro-'6,9-

methano-2,3,4-benzo [e] -dioxathipene-3-oxide [endosulphur hydride] chlorinated champhor [toxaphene] decachloroctahydro-l,3,4-metheno-2H-cyclobuta[e d] pentalen-Z-one dodecachloroctahydro-1,3,4-metheno-1H-cyclobuta[c d] pentalene [mirex] ethyl-1,1u,3,3a,4,5,5a,5a,6-decachloroctahydro-2- hydroxy-1,3,4-metheno-IH-cyclobutallc d] pentalene-Z- levulinate bis(pentachloro-2,4-cyclopentadien-l-yl) dinoctone-o 1,l-trichloro-2,2-bis(para-chlorophenyDether [DDT] dichlorodiphenyl-dichloroethane [TDE] di(para-chlorophenyl) -trichloromethylcarbinol [Dicofol] ethyl-4,4'-dichlorophenylglycolate [chlorobenzylate] ethyl-4,4-dibromobenzylate [bromobenzylate] ispropyl-4,4'-dichlorobenzylate 1,1,1-trichloro-2,2,bis(para-methoxyphenyl) ethane [methoxychlor] diethyl-diphenyl-dichloroethane decachloropentacyclo(3,3,2,O ,O ,O' )decan-4-one [chlordecon] NI'I ROPHENO-LS AN D DERIVATIVES 4,6-dinitro-6-methy1phenol, sodium salt [dinitrocresol] dinitrobutylphenol 2,2,2")-triethanolamine salt 2-cyclohexyl-4,6-dinitrophenol [dinex] 2-( l-methylheptyl) -4,6-dinitrophenyl-crotonate [dinocap] 2-sec.butyl-4,6-dinitrophenyl-3-methylbutenoate [binapacryl] 2-sec.butyl-4,6-dinitrophenyl-cyclopropionate 2-sec.butyl-4,6-dinitrophenylisopropylcarbonate [dinobuton] VARIOUS sabadilla rotenone cevadine veratridine ryania pyrethrin 3-allyl-2-methyl-4-oxo-2-cyclopenten-l-yl-chysanthemumate (allethrin) 6-chloropiperonyl-chrysanthemumate (barthrin) 2,4-dimethylbenzyl-chrysanthemumate (dimethrin) 2,3,4,5-tetrahydrophthalimidomethylchrysanthemumate (5-benzyl-3-furyl)-methyl-2,2-dimethyl-3-(Z-methylpropanyl) cyclopropanecarboxylate nicotine BACILLUS TH URINGEINSIS BE=RLINER dicyclohexylcarbodiimide diphenyldiimide [azobenzene] 4-chlorobenzyl-4-chlorophenylsulphide [chlorobenside] creosote oil 6-methyl-2-oxo-1,3-dithiolo- [4,5-b] -quinoxaline (quinomethionate) (I) -3- (2-furfuryl -2-methyl-4-oxocyclopent-2-enyl (I) (cis-trans) chrysanthemum-monocarb oxylate [furethrin] 2-pivaloyl-indane-1,3-dione [pindon] Z-fluoroethyl (4-bisphenyl) acetate 2-fluor0-N-methyl-N( l-naphthyl) -acetamide pentachlorophenol and salts 2,2,2-trichloro-N- (pentachlorophenyl) -acetimidoyl chloride N- 4-chloro-2-methylphenyl) -N,N-dimethylformamidine (chlorophenarnidine) 4-chlorobenzyl-4-fluorophenyl sulphide (fiuorbenside) 5,6-dichloro-l-phenoxycarbanyl-Z-trifluoromethylbenzimidazole (fenozaflor) tricyclohexyl tin hydroxide The new compounds of Formula I are prepared by a process similar to the Michaelis-Arbuzov reaction by reacting a compound of trivalent phosphorus of the formula in which R; and R have the meanings ascribed to them in Formula I, with a trichloroacetamide of the formula with elimination of R -Cl, when Y in Formula I stands for C1, or with a dichloroacetamide of the formula Cl\ Ill:

CH-C O-N-X-Bl G1 with elimination of R Cl, when Y in Formula I stands for H, R X and R having the meanings ascribed to them in Formula I.

The reaction is preferably carried out in a solvent that is inert to the reactants, for example, benzene, xylene, toluene, dioxane or cymene.

EXAMPLE 1 Preparation of starting products N-trichloroacetyl N acetanilide: 72.7 grams-of trichloroacetyl chloride were added dropwise within 30 minutes at 15 to 20 C. to a mixture of 54.1 grams (0.4 mol) of acetanilide +300 mols of toluene +405 grams of triethylamine, while stirring well. The reaction mixture was then stirred for 2 hours at room temperature. Triethylaminohydrochloride was removed by vacuum filtration and the solvent was distilled from the filtrate. 108 grams (96% of the theoretical yield). The residue was recrystallized from hexane. Yellowish crystals melting at 64 C.

For C H Cl NO .-Calculated (percent): Cl, 37.9; N, 5.0. Found (percent): Cl, 36.5; N, 5.1.

method:

i C CH Oil not capable I v I I f oi distillation o1 -N\'- i v f oooola or I I COCH:

. COCO]:

Cl MI. 135' C.

COCHa Cl N\ I COCCh CHz-CO M.P. 91 C.

N-COCCll CHr-CO CHI M-P. 101 C.

CHI M.P. 86 C.

COCO]: 1

EXAMPLE 2 Preparation of dichlorovinylphosphates of Formula I 0,0-dimethyl 1 (N-methyl N benzoylamino) -2,2- dichlorovinylphosphate [Compound No. 1]: 68.9 grams of N-methyl-N-trichloroacetylbenzamide were dissolved in 150 ml. of toluene. 31 grams of trimethylphosphite were added dropwise to this solution within 20 minutes. The temperature rose from 25 C. to 60 C. After completion of the exothermic reaction, the reaction mixture was kept at 70 C. for 2 hours. The solvent was removed by distillation and 85.5 grams (98.1% of the theoretical yield) of a yellowish brown oil remained that could not be distilled, even in a high vacuum. r 1.5220

[For C H C1 NO P.Calculated (percent): P, 8.8; N, 4.0. Found (percent): P, 8.7; N, 4.2.

The following compounds were produced by the same method Active principle No.

c) i J oiH.0)iP-.0-c=ocl. Highly i p I viscous oil.

I O i NCH:

'(CHIO)QP -;O'C=CCII Highly 'f l vlscousoll;

Q cooHi (CHIO)|PO--C;CCII Highly I ll viscous 011. o

coon, cl CH1. oil. cHio'- -o-o=cc1i' N doom (CH 0),l|-0C=O Ch Viscous oil.

N -01 JOCHa (CzH O)zP---OC=CCI: Highly ll viscous oil. 43 COCH! (C H O)zPO-C=C0h Highly H I viscous oil. 0 Q

COCH;

cirnoh -o-tho 012 Oil that can- II 8 o distilled.

coon. Cl

(cHio .P-oo=ocl oil that can- I notbe 0 N-C O--'O distilled amour-04 :0 01, MP. 101 0.

I /N\ V co co (cH|o),P-o-o=ooll 011m) l 1.4935. i co co Hr-AZH: I

(CzH O),P--OO=C 01. on m."

co co Biz-4BR:

' cmo ,1 -o-o=oc1, Cl on ma" Curio c1 (OH1O)1PO-C=CC11 Viscous 01 N-CO (c.m0)1P-o-c=oc1| Viscous on.

1 omens-043:0 01, MP. 120 0 N-CH3 I N03 (GH1'O)zP-O-C=CCh 011m" 1 1.5260. N-C oQ-cm 43H;

Preparation of mm. Hg.

Analysis for C H ClNO P.-Calcu1ated (percent):

N, 4.9; found (percent): N, 4.8. v

The following compounds of Formula II can be prepared in the same manner:

.P, 10.8; found (percent): P, 10.8. Calculated (percent):

Ra- R4 Property CH3 CH B.P. 86 C./0.02 mm. Hg. v x, CH CH B.P. 88 C./0.01 mm. Hg.

CH3 CH3 Oil. rt CHa CHa Oil. CH CH Oil. 02H; CH3 Viscoue oil; I CzHs CH3 Oil. CH; Reddlsh oil. ,CH; Oil. C a l- .5:

CH B.P. 100 C./0.001 mm. Hg? CH3 Viscous oil. 4 I CH; Do. CH Oil. CH; Oil. CH; H 85 (1/005 mm. Hg. OH; H 80 C./0.05 mm. Hg. I OH; H Oil. OH; H Oil. 02H H Viscous oil. 02H, H Oil. 1'; CzHs H Reddish yellow-oil. CzHa H Oil. C2H5 H Viscous oil. Cyclopropyl H Do.

a 5 H Oil. CH4C1(p) H Oil. CeHs CH3 O11. C H4Cl(p) CH; Yellow oil.

CH CH2 Brown oil. ,7 .7 1. 1. -CH CH\ CH1 CH and also those in which R and RC; form a ring together Parts of Bolus alba with 3.5 parts of sodium 1-benzyl-2 stearylbenzimidazole-6,3'-

-N\ /R'| Comp. no. R'r R: R; Property 72 021150 02H. (JO-CH: B.P. 90 0.10.01 mm. Hg.

GEE-CH2 Same as above Viscous oil.

... -do B.P. 90 C./0.02 mm. Hg.

.....do Do. (Hi

The following N-sulphonated compounds of Formula r Emulsion concentratez An emulsion concentrate can IV are prepared in an analogous manner: 00 be prepared in the following manner, using active principles having =good.solubility:

f A mixture is prepared from, 20 parts of active principle,

10 parts of xylene g i a 10 parts of a mixture consistin'g of a reaction product derived from an allrylphenol and ethylene oxide and R! Pwperty calcium dodecylbenzenesulphonate.

82%: 83 I 8%; gg on. An emulsion spray can prepared by diluting the mix- CzHs 00H; i a Do. ture to the requ1red concentration with water.

02m CH: --Ce i0 (n) 01 Granulates: 7.5 grams 0f one of the active principles V H of Formula I are dissolved in 100 ml. of acetone and the EXAMPLE 4 4 solution so obtainedisappliedto Q Z -grams of granulated Formulations attap'ulgite (mesh size 24/38 meshes per inch). The

Dusting preparations: Equal parts of one of the active 32?:i l ggggfik gifii ig gggg gi sggs g gg principles of the invention and precipitated silica are, finely content of 7 5% obtaine ground. Dusting preparation, preferably having an active principle content of 1 to 6%, can be prepared therefrom EjmMPLE 5 by admixture with kaolin or talcum. H

Wettable powder: To prepare a wettable powder, the j Coma 11191101163? n a g gf for x are med and A series of so1utions'"wereprepared 'by dissolving subey gmun stances 42, 43, 52, 57, 58; 72 and 74 in acetone. Six 50 parts of an active'principleof the invention solutions were prepared'o'fi each substance, the strengths 20 parts of highly adsorptive silica 75 being 1,000, 100, 10, 5, 225 and 1.25 ppm. of active 17 principle respectively. The bottom halvesof Petridishes were treated with 10 ml. each of the solutions. After the solvent had evaporated, supercooled-flies were placed in the Petri dishes and covered with the top halves of the dishes. Each dish contained 10 flies. After 1 hour, the- The active principles are applied in a concentration of 800 p.p.m. and the mortality in respect of all stages of development is assessed after 2 days and 7 days. In cases where a 100% kill is achieved after 2 days, the plant is re-infested.

5 degree of kill was assesed in respect of all concentrations.

I v After 2 days, After 7 days, Ceratitis capitata percent percent percent Substance 52 57 58 42 43 72 74 10 Adults Larvae Adults Larvae Comp. number: 100 100 100 100 100 100 100 42 100 100 100 60 100 100 100 100 100 100 100 100 100 100 00 100 100 100 100 100 100 100 0 0 100 so 100 100 100 .100 100 100 100 100 m0 100 0 40 100 100 50 100 50 100 100 100 100 100 0 100 100 50 50 50 50 H 4 r 3 :3 1&1 r3

EXAMPLE 6 Contact action on Apz's fabae EXAMPLE 9 Method: Young Vicia faba plants having a height of Efiect on ectoparasites and vectors about 6 cm are infested with parts of plants attacked by Aphis fabae. The conditions are right for the tests after (a) Rhipicephalus bursa: The tests are carried out with the plants have 'grown for a further 5 days and the aphid hungry adult ticks. Five ticks are introduced into each of population has increased accordingly. To test the contact the test-tubes and immersed for 1 to 2 minutes in 2 ml. action, the plants are sprayed from all sides with different of an aqueous emulsion containing 100 p.p.m. of the subconcentrations of the active principles, the maximum constance under test. Each tube is closed with a standardized centration being 800 p.p.m. The sprayer used is the kind plug of cotton wool and then inverted to allow the plug employed in chromatography. The action is assessed after to absorb the active-principle emulsion. Assessment is 2 days. made after 2 weeks.

The percentage of mortality in respect of the various A similar test is carried out with Rhipicephalus larvae. compounds is as follows: (b) Boophilus microplus (larvae): About 10 to 20 larvae are treated as per Test (a) with dilutions of an active principle. Assesment is made after 2 weeks. 7 42 4.3 53 74 m 17 (c) Lucilia sericata (larvae): A dilution series is pre- Percent pared from an emulsion concentrate of an active principle. 2 millilitres each of the concentrations are mixed with 2 grams of minced horsemeat in 10 ml. glass vessels. 20 to 00 i i% :33 i% i 30 of freshly hatched larvae are then introduced mto each 100 100 f the lass vessels. Assesment is made after 2 hours.

100 0 g (d) Aedes aegypti (larvae): L-l-larvae of the yellow fever mosquito are kept for 24 hours in 10 ml. each of different concentrations of an emulsifiable active-principle EXAMPLE 7 formulation. Assessment is then made. Action on larvae of Epilachna varivestis (e) Aedes aegypti (9 Adult mosquitoes are exposed Method: Young Phaseolus plants are immersed in agucfor l to a i g f' a solution a ous solutions of the active principles, the concentrations ,i gs gz ggggggz f if l i being 100, 400, 200 and 100 p.p.m. respect vegi.f Th: g As/dish gl 8 0 ar e presse in plants are allowed to dry and then each one is este with 5 larvae of Epilachna vorz'vestis at the L4 stage. Each g? ii i f g g gz :g ggggg': a g gg plant is covered with a plastic bag. kin S g1 mg a a The percentage kill in respect of the various compounds is assessed after 5 days.

TABLE L0 7 in p.p.m. or in mg. AS/dlsh 42 27 43 58 74 52 R. bursa B.1nicro- L. seri- A. aeaypi Percent plus cata,

Adult Larvae larvae larvae Larvae Adult 56 100 100 100 100 100 100 100 1 1% i% {3 3 gig 3:} 60 10 10 0.5 0.75 0.03 0.01 100 100 100 100 100 100 100 100 m 5 6 100 100 so e0 s0 s0 80 I m m 10 50 10 50 0.1 100 100 100 1.5 100 100 100 0.75 EXAMPLE 8 728 10g 5g g .22 I Effect on Tetranychus urticae I 8 lg 0 2g Method: Phaseolus plants at; the two-leaf -stage jre g :8 %g infested with Tetranychus urticae by contact with pieces 100 100 100 0.75 -of leaves attacked therewith, infestation being eifected 12 g3 1% 2 hours prior to treatment. .After l2 hours,. a populat on e 10 10 g 0.75 o g .00% comprising all stages is present in theplants. The active 8g 65 & principles in the form of a wettable powder are sprayed 1% 0 .72 0.522 0 a on the plants by means of a fine sprayer in a manner such 10 50 m that an even coating of droplets is formed on the surface v N H t d of the leaves. '75 es Minimum aimouutiqf actiyesuhsttance l 7 m n after 24 Mars I Peri- Phylloplaneta Blatta Tenebrio molztor *Dermestesfrlschii v dromia ameriorienaer manica ama. .tqljs Imago .,L ar.va Imago Larva larva larva granariua Comp. number:

3 wherein R is methoxy and R is methyl or wherein R 1s ethoxy and R is ethyl, and (2) a suitable carrier.

2. The composition of claim 1 in which R is methoxy and R is methyl.

3. The composition of claim 1 in which R; is cthoxy 40 and R is ethyl.

4. A method for combatting insects and nematodes R2 is ethyl.

wherein R 'is methoxy and R i is methylor wherein'R is ethoxy and R is ethylt= v I 5. The methoxy of claim 4 in which R; is methoxy and R is methyl. a 6. The method of claim 4 in which R; is ethoxy and References Cited UNITED STATES PATENTS 3,183,258 5/1965 Schuler et a1. 260-3265 A TALBERT MEYERS; Primary Examiner A I. ROBINSON, Assistant Examiner 

